JP2022519303A - One-component encapsulant or adhesive composition - Google Patents

Abstract

A method for preparing a prepolymer containing a urethane group and a curable silicon functional group, and a prepolymer of formula (IV) (wherein variable elements are defined as described in the claims) are provided. The prepolymer may be cured by ambient moisture to form a crosslinked polymer and is therefore suitable for use as a component of a one-component encapsulant or adhesive composition. TIFF2022519303000038.tif24161 [Selection diagram] None

Description

The present invention relates to a method for preparing a prepolymer containing a urethane group and a curable silicon functional group, a prepolymer containing the group, and its use as a component of a one-component encapsulant or adhesive composition. Further, the present invention relates to a method for preparing a crosslinked polymer containing a urethane group and a siloxane bond having a silicon content of 0.001 to 0.3 mol per 100 g of the crosslinked polymer, and a crosslinked polymer containing a urethane group and a siloxane bond.

Polyurethane is an important industrial polymer. Polyurethanes have very good mechanical properties and are therefore used in many technical applications, for example as foams or as binders or resins for coatings or adhesives.

Polyurethane is specifically modified with a silyl group, which is an alkoxysilane group. Such silyl-modified polyurethanes are moisture curable and are used, for example, as one component (1K) binders in coatings, adhesives or encapsulants.

The one-component encapsulant can be prepared by various means. For example, the silane-terminated prepolymer may be converted to a siloxane after hydrolysis under humidity. A known system is, for example, Kaneka's MS-polymer based on the silane-terminated polyether described in US Pat. No. 3,971,751.

Another class of sealants is the so-called SPUR (Silane-PUR Hybrid), a silane-modified polyurethane that is becoming increasingly attractive to manufacturers of adhesives, sealants and coatings. The high performance hybrid technology is the result of a synergistic effect between the curing mechanism of silane and the properties of the polyurethane backbone, i.e. good mechanical and performance properties. Formulations based on silane-terminated polyurethane allow, for example, fast curing at room temperature, good durability, curing with minimal gas release, and an increase in the variety of additives and adhesion promoters.

According to US Pat. No. 3,632,557, a silicon-terminated polyurethane is obtained by reacting an isocyanate-terminated prepolymer with aminosilane. Such polymers tend to have a high viscosity due to the presence of urea groups.

US Pat. No. 4,625,012 and US Pat. No. 6,355,127 disclose methods for obtaining silyl-modified polyurethanes using isocyanate-organosilanes. Such polymers also tend to have high viscosities and low elongation.

In WO 2012/003187, polyurethanes are modified using silicon compounds with hydrogen-silicon bonds and crosslinkable groups.

The object of European Patent No. 2648791 is an epoxy composition containing a compound having a 5-membered cyclic ring system containing oxygen and sulfur, in particular 1,3-oxathiolan-2-thione.

D.D. Reynolds, D.L. Fields and D.L. Johnson, Journal of Organic Chemistry, 1961, pages 5111 to 5115 discloses compounds having a 5-membered cyclic monothio-carbonate ring system and their reactions. In particular, the reaction with amino compounds is mentioned.

WO 2019/034468 and WO 2019/034469 relate to methods of synthesizing compounds having at least one monothiocarbonate group.

WO 2019/034470 and WO 2019/034473 relate to polymers obtained by reacting compounds with at least one monothiocarbonate group.

The use of structural units based on polyether as soft segments of encapsulants is well established, as described, for example, in US Pat. No. 6,103,850.

However, additional heteroatoms or functionality that allow prepolymers with urethane and moisture curable silyl groups, in particular the technical applications of said polymers to be improved and / or expanded in the field of technical applications. There is still a need for polymers with. In addition, there is a need for methods of preparing silyl-modified polyurethanes without the use of isocyanates to avoid toxicological problems.

U.S. Pat. No. 3,632,557 U.S. Pat. No. 4,625,012 U.S. Pat. No. 6,355,127 International Publication No. 2012/003187 European Patent No. 2468791 International Publication No. 2019/034468 International Publication No. 2019/034469 International Release No. 2019/034470 International Publication No. 2019/034473 U.S. Pat. No. 6,103,850

D.D. Reynolds, D.L. Fields and D.L. Johnson, Journal of Organic Chemistry, 1961, pages 5111 to 5115

Therefore, it is an object of the present invention to provide an economical and adaptable method for preparing a silyl-terminated urethane group-containing prepolymer.

Further, an object of the present invention is to provide a silyl-terminated urethane group-containing prepolymer that is stable under anhydrous conditions, allows rapid curing at room temperature when exposed to moisture, and is suitable for a variety of technical applications. That is.

Further, an object of the present invention is to provide a silyl-modified urethane group-containing polymer suitable for use in various technical applications.

Furthermore, it is an object of the present invention to provide an economical and adaptable method for preparing a silyl-modified urethane group-containing polymer.

It has now been found that the use of cyclic thiocarbonates provides a unique cost-effective way to obtain polymer hybrids containing urethane units and thioether units or disulfide units combined with silane functionality. Was done. Such prepolymers are particularly suitable for use in one-component encapsulants or adhesive compositions with improved properties such as improved chemical stability, improved refractive index and transparency.

Therefore, in the first aspect, the present invention is a method for preparing a prepolymer containing a urethane group and a curable silicon functional group.
a) Compounds with at least one 5-membered cyclic monothiocarbonate group A),
And compounds with at least one amino group selected from a primary or secondary amino group or a blocked primary or secondary amino group B),
And optionally compound C with at least one functional group that reacts with the group-SH)
The process of using as a starting material,
Here, at least one of the compounds used as a starting material contains a silicon functional group.
And compounds A), B) and optionally C),
b) The present invention relates to a method comprising a step of reacting compounds A) and B) and optionally C) under the exclusion of water to obtain a prepolymer having a curable silicon functional group.

In a further aspect, the invention relates to a prepolymer comprising a urethane group and a curable silicon functional group available by method steps a) and b) as defined in any aspect of the specification.

In a further aspect, the invention
Equation (a)

Based on, and
(b) Regarding prepolymers containing curable silicon functional groups.

In a further aspect, the invention relates to a composition comprising a prepolymer as defined in any aspect of the specification, in particular a one-component encapsulant or adhesive composition.

In a further aspect, the invention relates to the use of the prepolymer as defined in any aspect of the present specification as a component of a composition, preferably a one-component encapsulant or adhesive composition.

In a further aspect, the invention is a crosslinked polymer comprising monomer units derived from compound A), compound B) and optionally compound C), wherein the polymer comprises 0.001 to 0.3 mol of silicon per 100 g of the crosslinked polymer. It relates to a crosslinked polymer as defined in any aspect of the present specification.

In a further aspect, the invention is a method of preparing a crosslinked polymer containing a urethane group and a siloxane bond.
Steps a) and b) as defined in any one of claims 1 to 10, and
b2) The present invention relates to a method comprising a step of applying the prepolymer obtained in b) to a surface, voids or a three-dimensional mold and curing the silicon functional group with ambient moisture.

In a further aspect, the invention relates to a crosslinked polymer available by method steps a), b) and b2) as defined in any aspect of the specification.

As used herein, the term "polymer hybrid" means a polymer having both a cured inorganic network and a cured organic network.

As used herein, the term "one-component encapsulant composition" means a composition containing a prepolymer having a curable group that is intended to be applied to a surface / substrate. ..

As used herein, the term "one-component adhesive composition" means a composition containing a prepolymer having a curable group that is intended to be applied between two substrates.

As used herein, the term "encapsulant" means a composition containing a crosslinked polymer that is ultimately applied to the surface / substrate.

As used herein, the term "adhesive" means a composition containing a crosslinked polymer that is ultimately applied between two substrates.

As used herein, the singular articles "a," "an," and "the" include the plural unless the content specifically dictates otherwise.

FIG. 1 is a graph showing a transmission spectrum from 200 to 1000 nm (dashed line: Example 8 between two glass plates, solid line: two glass plates for comparison).

The method of the present invention for preparing a prepolymer containing a urethane group and a curable silicon functional group is carried out by compound A), compound B) and optionally compound C). In general, prepolymers contain S-functional groups, especially thioether groups and / or disulfide groups.

The method of the present invention also provides a composition comprising one or more prepolymers comprising a urethane group and a curable silicon functional group.

Therefore, in a further aspect, the present invention is a method of preparing a composition containing one or more prepolymers containing a urethane group and a curable silicon functional group.
a) Compounds with at least one 5-membered cyclic monothiocarbonate group A),
And compounds with at least one amino group selected from primary or secondary amino groups or blocked primary or secondary amino groups B),
And optionally compound C with at least one functional group that reacts with the group-SH)
The process of using as a starting material,
Here, at least one of the compounds used as a starting material contains a silicon functional group.
And compounds A), B) and optionally C),
b) The process of reacting compounds A) and B) and optionally C) under the elimination of water to obtain a composition containing one or more prepolymers with curable silicon functional groups. Regarding how to include.

Compound A) contains at least one 5-membered cyclic monothiocarbonate group.

A 5-membered cyclic monothiocarbonate group is a 5-membered ring system, 3 of which are derived from monothiocarbonate-OC (= O) -S-, and 2 members are 5-membered rings. It is a closed carbon atom.

Compound A) may be a small molecule compound or a polymer compound, and may contain, for example, up to 1000, particularly up to 500, preferably up to 100 5-membered cyclic monothiocarbonate groups.

In a preferred embodiment, compound A) comprises 1 to 3 cyclic monothiocarbonate groups.

In the most preferred embodiment, compound A) comprises one or two 5-membered cyclic monothiocarbonate groups.

Preferred compound A) has a molecular weight of up to 10000 g / mol, especially up to 5000 g / mol, especially up to 1000 g / mol. Compound A) having a molecular weight of up to 500 g / mol is most preferable.

Compound A) may contain other functional groups such as a non-aromatic ethylenically unsaturated group, an ether group, a thioether group or a carboxylic acid ester group or a silicon functional group.

In a preferred embodiment, compound A) is free of functional groups other than cyclic monothiocarbonate groups, non-aromatic ethylenically unsaturated groups, ether groups, thioether groups, carboxylic acid ester groups or silicon functional groups.

Preferred compound A) is a compound of formula (I) and / or formula (II).

The preferred compound A) is of the formula

(During the ceremony,
R ^1a to R ^4a are independent hydrogen or organic groups with up to 50 carbon atoms.
Alternatively, the two carbon atoms of the R ^2a , R ^4a and thiocarbonate groups may also be combined to form a 5-10 membered carbon ring).
Compound or formula

(During the ceremony,
R ^1b to R ^4b are independent hydrogen or organic groups with up to 50 carbon atoms.
Alternatively, the two carbon atoms of the R ^2b , R ^4b and monothiocarbonate groups may also be combined to form a 5-10 membered carbon ring.
One of the groups R ^1b to R ^4b is a linking group to Z,
n is an integer of at least 2
Z is an n-valent organic group)
It is a compound of.

Compound A) of formula (I) has only one 5-membered cyclic monothiocarbonate group.

When any of R ^1a to R ^4a is an organic group, such an organic group is preferably an organic group having a maximum of 30 carbon atoms, more preferably a maximum of 20 carbon atoms.

In a more preferred embodiment, R ^2a and R ^4a do not combine with the two carbon atoms of the thiocarbonate group to form a 5- to 10-membered carbon ring.

When any of R ^1a to R ^4a is an organic group, such an organic group may contain a heteroatom and a functional group. Examples of functional groups are, for example, non-aromatic ethylenically unsaturated groups, ether groups, thioether groups, carboxylic acid ester groups or silicon functional groups. As a suitable heteroatom, the organic group may contain O, N, S, Si and / or Cl. R ^1a to R ^4a may contain oxygen in the form of, for example, an ether group, a hydroxy group, an aldehyde group, a keto group or a carboxy group. In a preferred embodiment, the organic group is an aliphatic organic group having up to 30 carbon atoms which can contain O, N or Cl, especially oxygen.

The reacted compound A) in the prepolymer or composition comprising the prepolymer should be compatible with the curable silicon functional group, i.e. stable under anhydrous conditions.

In a more preferred embodiment, the organic group is selected from the alkyl group, the group -CH ₂ -OR ^5a or the group -CH ₂ -OC (= O) -R ^6a or the group -CH ₂ -NR ^7a R ^8a , R ^5a . ~ R ^8a is an organic group having a maximum of 30 carbon atoms, preferably a maximum of 20 carbon atoms. In particular, R ^5a to R ^8a are aliphatic or aromatic groups that can contain oxygen, for example in the form of ether groups. In a preferred embodiment, R ^5a to R ^8a are aliphatic hydrocarbon groups, such as alkyl groups, alkoxy groups or polyalkyleneoxy groups having 1 to 10 carbon atoms. In the most preferred embodiment, R ^5a to R ^8a are aliphatic hydrocarbon groups, particularly alkyl groups having 1 to 10 carbon atoms.

In the most preferred embodiment, the organic group is an alkyl group, group -CH ₂ -OR ^5a or group -CH ₂ -OC (= O) -R ^6a , where R ^5a and R ^6a contain 1-10 carbon atoms. It is an alkyl group having.

Preferably, all 2 to 4 of R ^1a to R ^4a in the formula (I) are H, and the remaining groups R ^1a to R ^4a are organic groups.

More preferably, two or three of R ^1a to R ^4a in the formula (I) are H, and the remaining groups R ^1a to R ^4a are organic groups, particularly alkyl groups, groups -CH ₂ -OR ^5a or. The group is -CH ₂ -OC (= O) -R ^6a .

Most preferably, three of R ^1a to R ^4a in the formula (I) are H, and the remaining groups of R ^1a to R ^4a are organic groups. In a preferred embodiment, R ^1a or R ^2a is an organic group, particularly an alkyl group, the remaining group representing the group -CH ₂ -OR ^5a or the group -CH ₂ -OC (= O) -R ^6a .

As the preferred compound A) having one 5-membered cyclic monothiocarbonate group, for example, the formula

Compound A) can be mentioned.

Substituent "C _12/14 " means a substituent derived _{from C 12 / C 14 fatty alcohol} .

Compound A) of formula (II) has at least two 5-membered cyclic monothiocarbonate groups.

When any of R ^1b to R ^4b is an organic group, such an organic group is preferably an organic group having a maximum of 30 carbon atoms. In a more preferred embodiment, R ^2b and R ^4b do not combine with the two carbon atoms of the thiocarbonate group to form a 5- to 10-membered carbon ring.

If any of R ^1b to R ^4b is an organic group, such an organic group may contain other elements other than carbon and hydrogen. In particular, the organic group may contain O, N, S, Si or Cl. In a preferred embodiment, the organic group may contain O or Cl. R ^1b to R ^4b may contain oxygen in the form of, for example, an ether group, a hydroxy group, an aldehyde group, a keto group or a carboxy group.

The reacted compound A) in the prepolymer or composition comprising the prepolymer should be compatible with the curable silicon functional group, i.e. stable under anhydrous conditions.

One of the groups R ^1b to R ^4b is a linking group to Z.

Preferably, the linking group is a single bond or a group selected from -CH _{2-, -CH 2-O-, -CH 2-OC (= O)-or -CH 2- -NR 5b- ,} ^{where R 5b is} . Aliphatic groups, especially alkyl groups with up to 20 carbon atoms.

More preferably, the linking group is a single bond or a group selected from -CH _{2-, -CH 2-O- or -CH 2 - OC} (= O)-. In the most preferred embodiment, the linking group is the group -CH ₂ -O-.

Preferably, two or three of the groups R ^1b to R ^4b in formula (II) are H.

In the most preferred embodiment, the three groups R ^1b to R ^4b represent H and the remaining groups R ^1b to R ^4b are linking groups to Z.

In the most preferred embodiment, the group R ^1b or R ^2b is a linking group to Z.

n is an integer of at least 2. For example, n may be an integer from 2 to 1000, especially 2 to 100, especially 2 to 10.

In a preferred embodiment, n is an integer of 2-5, in particular n is 2 or 3.

In the most preferred embodiment, n is 2.

Z is an n-valent organic group. When n is a large number, for example 10-1000, Z is a polymer group, particularly a polymer group obtained by radical polymerization, polycondensation or polyaddition of a polymer backbone, such as polymerization or copolymerization, eg, ethylenically unsaturated monomers. It may be a polymer skeleton. For example, polyester or polyamide is obtained by polycondensation under the desorption of water or alcohol, and polyurethane or polyurea is obtained by heavy addition.

Such compounds of formula (II) are polymers obtained, for example, by radical polymerization or copolymerization of an ethylenically unsaturated monomer containing a monothiocarbonate group, or a monomer containing an epoxy group that is subsequently converted to a monothiocarbonate group. be.

In a preferred embodiment, Z is an n-valent organic group having up to 50 carbon atoms, particularly up to 30 carbon atoms and may contain other elements other than carbon and hydrogen, where n is 2-5. An integer of, especially 2 or 3, most preferably 2.

In a particularly preferred embodiment, Z is an n-valent organic group having up to 50 carbon atoms, especially up to 30 carbon atoms, containing only carbon, hydrogen and optionally oxygen and no additional elements. , N is an integer from 2 to 5, especially 2 or 3, most preferably 2.

In a preferred embodiment, Z is the formula
(VO-) _m V (G1)
(During the ceremony,
V is a C ₂ to C ₂₀ alkylene group, m is an integer of at least 1)
It is a polyalkoxylen group of. The terminal alkylene group V is attached to a linking group which is one of the groups R ^1b to R ^4b .

Preferably, the C ₂ to C ₂₀ alkylene group is a C ₂ to C ₄ alkylene group, particularly ethylene or propylene. m may be, for example, an integer of 1 to 100, particularly 1 to 50.

In a more preferred embodiment, Z is the formula

(During the ceremony,
W is a divalent organic group with a maximum of 10 carbon atoms, n is 2 (in equation (II)), and R ^10b to R ^17b are H or C ₁ to C ₄ independently of each other. It is an alkyl group, and the two hydrogen atoms at the para position with respect to W are replaced by a bond to the linking group, which is one of the groups R ^1b to R ^4b ).
It is the basis of divalent.

Preferably, at least 6 of R ^10b to R ^17b are H. In the most preferred embodiment, all of R ^10b to R ^17b are H.

The group W is, for example, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (C ₂ H ₅ )-or -SO _2- .

Preferably, W is an organic group consisting only of carbon and hydrogen.

Most preferably, W is C (CH ₃ ) ₂ , which corresponds to the structure of bisphenol A.

In a more preferred embodiment, Z is a group G3 and G3 is an alkylene group, in particular a C ₂ to C ₈ alkylene group. Preferred examples of such alkylene groups are ethylene (CH ₂ -CH ₂ ), n-propylene (CH ₂ -CH ₂ -CH ₂ ), especially n-butylene (CH ₂ -CH ₂ -CH ₂ -CH ₂ ). be.

Compound A) having at least two 5-membered cyclic monothiocarbonate groups is, for example, the formula.

(In the formula, G represents an alkylene group having 2 to 10 carbon atoms, especially 2 to 6 carbon atoms).
It is a compound of.

Preferred compounds of formula (IIa) are of formula (IIa).

Bis-1,3-oxathiolan-2-one-5,5'-[1,4-butanjiylbis (oxymethylene)] with.

Compound A) may be a mixture of different compounds A).

Mixtures of different compounds A) are one or more compounds of formula (I), preferably one or two formulas (I), particularly compounds of formulas (Ia)-(Ie), or compounds of formula (I). It may be a mixture of A) and formula (II), eg, compound A) of formula (IIa), in particular of formula (IIb).

A mixture of compound A) of formula (I) is more preferred, where the three R ^1a to R ^4a in formula (I) are hydrogen and the remaining groups of R ^1a to R ^4a are organic groups. ,
R ^1a or R ^2a is the remaining group representing an organic group, particularly an alkyl group, group -CH ₂ -OR ^5a or group -CH ₂ -OC (= O) -R ^6a .
R ^5a and R ^6a are alkyl groups having 1 to 10 carbon atoms.

Formula (I) can be present in an amount of up to 30% by weight (wt%), preferably up to 20 wt%, based on the total weight of compound A) of formula (I), eg formula (IIa). , In particular a mixture with compound A) of formula (IIb) is more preferred.

More preferably, a mixture of the compound A) of the formula (I), particularly a mixture of the compounds A) of the formulas (Ia) to (Ie), particularly a mixture of the compounds of the formulas (Ia) to (Ic) is used.

The mixture of compound A) and compound A), respectively, is a liquid at 21 ° C. and 1 bar. In one preferred embodiment, liquid compound A) is obtained by dissolving compound A), which is solid at 21 ° C., 1 bar, in compound A), which is liquid at 21 ° C., 1 bar.

In a preferred embodiment, compound A) is a liquid at 21 ° C., 1 bar.

Some methods of synthesizing compound A) with one monothiocarbonate group have been described in the prior art.

According to US Pat. No. 3,072,676 and US Pat. No. 3,201,416, ethylene monothiocarbonate can be prepared by a two-step method. In the first step, mercaptoethanol and chlorocarboxylate are reacted to obtain hydroxyethylthiocarbonate, which is heated in the presence of a metal salt catalyst in the second step to obtain ethylene monothiocarbonate.

According to U.S. Pat. No. 3,517,029, alkylene monothiocarbonate is obtained by reacting mercaptoethanol with a carbonate diester in the presence of a catalytically active salt of thorium.

According to the method disclosed in US Pat. No. 3,349,100, an alkylene monothiocarbonate is obtained by reacting an epoxide with carbonyl sulfide. The availability of carbonyl sulfide is limited. The yield and selectivity of the obtained alkylene monothiocarbonate is low.

Synthesis using phosgene as a starting material is known from US Pat. No. 2,828,318. React phosgene with hydroxymercaptan. The yield of monothiocarbonate is still low and by-products from the polymerization are observed.

The preferred method for preparing compounds A) and C) is
a) Using a compound having at least one epoxy group (simply referred to as an epoxy compound) as a starting material,
b) The adduct is obtained by reacting the compound with phosgene or alkyl chloroformate.
c) React the adduct with a compound containing anionic sulfur to give a compound with at least one 5-membered cyclic monothiocarbonate group.
The method.

This method is detailed in WO 2019/034469.

Compound B) is a compound having at least one amino group selected from a primary or secondary amino group or a blocked primary or secondary group. As used herein, the term "amino group" means a primary or secondary amino group unless otherwise indicated or otherwise unclear from the content.

Compound B) does not contain any monothiocarbonate group.

Compound B) may have, for example, a molecular weight of up to 500,000 g / mol. This may be the case when compound B) is a polymer compound, for example a polymer containing an amino group.

For polymers, the term "molecular weight" as used herein generally means a number average molecular weight Mn as determined by gel permeation chromatography (GPC) with respect to polystyrene as a standard.

Compound B) may be an adduct, for example, an adduct containing a urethane group obtained by reacting a compound having a cyclic monothiocarbonate group with a compound having a primary or secondary amino group. Here, the amino group is a chemical excess compared to the monothiocarbonate group, and thus still has a primary or secondary amino group, but is essentially a urethane group that does not have a monothiocarbonate group. Additives containing are obtained.

Preferred compound B) has a molecular weight of up to 10000 g / mol, especially up to 5000 g / mol, especially up to 1000 g / mol. Compound B) having a molecular weight of 60 g / mol to 500 g / mol is most preferable.

Compound B) may contain, for example, a polymerizable ethylenically unsaturated group, an ether group or a carboxylic acid ester group, or a silicon functional group.

In a preferred embodiment, compound B) does not contain any other functional group other than a primary or secondary amino group, a tertiary amino group, a polymerizable ethylenically unsaturated group, an ether group or a silicon functional group. ..

In a preferred embodiment, compound B) contains 1 to 10 amino groups, preferably 1 to 5, each 1 to 3 amino groups, and in the most preferred embodiment, compound B) contains 1 to 2 amino groups. Contains amino groups.

In a preferred embodiment, at least one amino group of compound B) is a primary amino group.

In the most preferred embodiment, all amino groups of compound B) are primary amino groups.

The compound B) having one amino group is, for example, a monoalkylamine having a primary amino group, for example, C ₁ to C ₂₀ alkylamine or a cycloalkylamine or an etheramine, for example, 2-methoxyethylamine or 3-methoxypropyl. Amines or di or polyether amines, such as di or polyglycol amines, polyoxypropylene amines.

Compound B) having more than one amino group is, for example,
--Alkylene-diamine or alkylene-polyamine, such as ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, neopentanediamine, octamethylenediamine, 1,3-diaminopentane, 2-methylpentane-1,5- Diamine, or 1,1,1-tris (aminomethyl) ethane,
—— An alkylene-diamine or alkylene-polyamine (polyetheramine) containing an ether group, such as polyglycoldiamine or polyoxypropylenediamine,
--Alicyclic diamines such as cyclohexyldiamine, such as 1,2-diamino-cyclohexane, 1-methyl-2,4-diaminocyclohexane, 1-methyl-2,6-diaminocyclohexane or mixtures thereof, isophoronediamine, bis ( 4-Amino-cyclohexyl) methane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5-bisaminomethyl-tetrahexane or 3,3'-dimethyl-4,4 'Diamino-dicyclohexanemethane,
--Aromatic diamines such as 1,2-phenylenediamine or 1,4 phenylenediamine, toluenediamine, 4,4'diamino-diphenylmethane, 4,4'diaminodiphenyl sulfone, 2,5-bisaminomethyl-furan.

Compound B) may also be used in a form in which the amino group is protected by a protecting group. As soon as it is needed or desired, the protecting group is removed, resulting in the above compound B) having a free amino group. Removal of protecting groups usually occurs under reaction conditions. Amino groups normally protected with respect to amino groups are, for example, ketimine, aldimine, imidazolidine, oxazolidine, Lewis acid complexed amines, carbamate, benzyloxycarbonylamine, acyloxime or formanilide. The deprotection reaction can be triggered, for example, by either temperature, light, pH or the presence of moisture / humidity.

Further suitable compounds B) are listed, for example, in WO 2019/034470 and WO 2019/034473.

Compound B) may be a mixture of different compounds B).

Compound C) is a compound having at least one functional group that reacts with the thiol group-SH.

Compound C) does not contain a 5-membered cyclic monothiocarbonate group and does not contain an amino group.

Compound C) may have, for example, a molecular weight of up to 500,000 g / mol. This may be the case if compound C) is a polymer compound, eg a polymer.

The preferred compound C) has a molecular weight of up to 10000 g / mol, especially up to 5000 g / mol, especially up to 1000 g / mol. Compound C) having a molecular weight of 60 g / mol to 500 g / mol is most preferable.

Compound C) may have, for example, up to 1000 functional groups that react with group-SH, in particular up to 500, preferably up to 100 functional groups that react with group-SH.

In a preferred embodiment, compound C) comprises 1-10 functional groups that react with 2-6 groups-SH in particular.

In the most preferred embodiment, compound C) comprises a functional group that reacts with two or three groups-SH.

In a preferred embodiment, the reaction of the functional group of compound C) with the group-SH results in the formation of a sulfur-carbon bond.

The reaction between the functional group of compound C) and the group-SH may be an addition reaction, a condensation reaction or a nucleophilic substitution reaction.

The compound C) that undergoes an addition reaction with the group-SH is, for example, a compound having a non-aromatic ethylenically unsaturated group, a compound having an epoxy group, or a compound having an isocyanate group as a functional group. Non-aromatic ethylenically unsaturated groups are non-aromatic carbon-carbon double bonds or carbon-carbon triple bonds.

The compound C) that undergoes a condensation reaction with a group-SH is, for example, a compound having a carbonyl group as a functional group, for example, a monocarbonyl compound or a dicarbonyl compound, for example, a dialdehyde or a diketone.

The compound C) that undergoes a nucleophilic substitution reaction with the group-SH is, for example, a compound having a halide, particularly a chloride, as a functional group.

As used herein, the term << halide >> is a common name for a covalently bonded halogen atom, preferably a Cl atom. As used herein, the term "chloride" is a common name for covalently bonded Cl atoms.

Preferred functional groups that react with group-SH are non-aromatic ethylenically unsaturated groups or epoxy groups, more preferably non-aromatic ethylenically unsaturated groups.

Preferred examples of polymerizable ethylenically unsaturated groups are vinyl group H ₂ C = CH-, ethynyl group HC≡C-, olefin group -HC = CH-, and each of the two carbon atoms in the double bond is 1 Substituents are substituted with only one hydrogen, especially with carbon atoms containing ring carbon atoms, groups -C≡C-, and acrylic or methacrylic groups (simply referred to as (meth) acrylic groups). be. The term "vinyl group" as used herein does not include (meth) acrylic groups.

A more preferred compound C) is a compound having a vinyl group, a (meth) acrylic group or an epoxy group, most preferably a vinyl group, an ethynyl group or a (meth) acrylic group, particularly a (meth) acrylic group, particularly a methacryl group.

The reacted compound C) in the prepolymer or composition comprising the prepolymer should be compatible with the curable silicon functional group, i.e. stable under anhydrous conditions.

Compounds having a vinyl group, a (meth) acrylic group or an epoxy group are well known.

Suitable compounds C) are listed, for example, in WO 2019/034470 and WO 2019/034473.

Compound C) is a urethane group-containing adduct obtained by reacting an adduct, for example, a hydroxy-substituted (meth) acrylic acid ester with an alkylene diisocyanate to produce a urethane group-containing adduct having a terminal (meth) acrylate group. It may be a thing. Suitable compounds are, for example, diurethane dimethacrylate. Adducts are also available by reacting with hydroxy-substituted vinyl compounds.

Compound C) may be a mixture of different compounds C).

At least one of the compounds to be reacted contains a silicon functional group.

When compounds A) and B) are reacted, at least one of compounds A) or B) contains a silicon functional group.

When compounds A), B) and C) are reacted, at least one of compounds A), B) or C) contains a silicon functional group.

More than one of A) and B), A), B) and C), respectively, may contain a silicon functional group. Preferably, only one of the compounds to be reacted is a compound containing a silicon functional group.

As mentioned above herein, compounds A), B) and C) may be mixtures of different compounds A), B) and C). Therefore, a mixture of a compound having a silicon functional group and a compound having no silicon functional group is used to obtain the desired content of the silicon functional group in the compound obtained from the compounds A), B) and optionally C). It can be easily obtained by doing so.

In a preferred embodiment, compound B) or compound C) comprises a silicon functional group.

A silicon functional group is preferably a group having at least one silicon atom and a group capable of cross-linking by at least one silanol cross-linking reaction.

The silicon functional group may contain more than one silicon atom. Silicon atoms may be bonded to each other either directly or via oxygen cross-linking. In a preferred embodiment, the silicon functional group contains 1 to 3 silicon atoms. Most preferably, a silicon functional group having only one silicon atom.

The group that can be crosslinked by the silanol cross-linking reaction is preferably a hydroxy group and a hydrolyzable group, particularly an alkoxy group, and an alkoxy group, particularly a C ₁ to C ₁₀ alkoxy group is preferable.

The silicon functional group may contain more than one group that can be crosslinked by a silanol cross-linking reaction. The possible number of groups that can be crosslinked by the silanol cross-linking reaction depends on the number of silicon atoms in the silicon functional group.

The silicon functional group may further contain a hydrogen, alkyl or alkylene-vinyl group attached to the silicon atom. In a preferred embodiment, the silicon functional group may contain an alkyl or alkylene-vinyl group, but does not contain hydrogen attached to a silicon atom.

Preferably, the silicon functional group is any other than silicon, a group capable of cross-linking by silanol cross-linking reaction, hydrogen, alkyl or alkylene-vinyl groups bonded to silicon and oxygen as a possible cross-link between silicon atoms. Does not contain other components.

More preferably, the silicon functional group is of the formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
At least one of the groups R ^1s to R ^3s is an alkoxy group, and the other groups R ^1s to R ^3s are hydrogen, alkyl or alkylene-vinyl groups).
Alkoxysilane group.

Most preferably, the silicon functional group is of the formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
At least one of the groups R ^1s to R ^3s is an alkoxy group, and the other groups R ^1s to R ^3s are an alkyl group or an alkylene-vinyl group, particularly one alkyl group).
Alkoxysilane group.

The alkoxy group is preferably a C ₁ to C ₁₀ alkoxy group, particularly a C ₁ to C ₄ alkoxy group, such as butoxy, propoxy, ethoxy or methoxy group. Most preferably, the alkoxy group is an ethoxy or methoxy group.

The alkyl group is preferably a C ₁ to C ₁₀ alkyl group, particularly a C ₁ to C ₄ alkyl group, such as a butyl, n-propyl, ethyl or methyl group. Most preferably, the alkyl group is an ethyl or methyl group.

The alkylene-vinyl group is preferably a C ₂ to C ₈ alkylene-vinyl group, particularly a C ₁ to C ₂ alkylene-vinyl group, and more preferably a vinyl or allyl group.

Preferably, two or three of the groups R ^1s to R ^3s are alkoxy groups, and the remaining groups R ^1s to R ^3s are hydrogen, alkyl or alkylene-vinyl groups.

More preferably, two or three groups R ^1s to R ^3s are alkoxy groups, and any remaining groups R ^1s to R ^3s are alkyl or alkylene-vinyl groups. For example, two or three of the groups R ^1s to R ^3s are methoxy or ethoxy, and any remaining groups R ^1s to R ^3s are methyl, ethyl, vinyl or allyl.

Most preferably, the two groups R ^1s to R ^3s are alkoxy groups, and any remaining groups R ^1s to R ^3s are alkyl or alkylene-vinyl groups, preferably alkyl groups.

Preferred compounds A) with silicon functional groups are one or two 5-membered cyclic monothiocarbonate groups, particularly one 5-membered cyclic monothiocarbonate group and one alkoxysilane group-SiR ^1s R ^2s . Including R ^3s .

Particularly preferred compounds are formula (VII).

(In the formula, R ^1s to R ^3s have the above meanings, Sp is an organic group having 1 to 20, particularly 1 to 10, preferably 1 to 6, particularly 1 to 3 carbon atoms. There is a spacer group)
It is a compound of. Sp may contain atoms other than carbon and hydrogen, such as nitrogen, oxygen or sulfur. Preferably, Sp is a hydrocarbon group that may contain oxygen, for example in the form of an ether group, but no other heteroatoms. In a particularly preferred embodiment, Sp is an alkylene group having 1 to 20, particularly 1 to 10, most preferably 1 to 6, particularly 1 to 3 carbon atoms.

Specific examples of compounds of formula (VIIa) include:

It is a compound of.

The compound of formula (VII) can be prepared by the method described in WO 2019/024469.

Preferred compounds B) with silicon functional groups include one or two amino groups, in particular one amino group and one alkoxysilane group-Si R ^1s R ^2s R ^3s .

Suitable examples of compound B) having a silicon functional group are 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3- (N, N-dimethylaminopropyl) aminopropylmethyldimethoxysilane or 3- ( N, N-dimethylaminopropyl) Aminopropyltrimethoxysilane.

A preferred compound C) having a silicon functional group comprises one or two functional groups that react with the group-SH and one alkoxysilane group-Si R ^1s R ^2s R ^3s .

Suitable examples of compound C) having a silicon functional group are 3-trimethoxysilylpropylmethacrylate, 3- (dimethoxymethylsilyl) propylmethacrylate, trimethoxysilylpropylacrylate or 3- (dimethoxymethylsilyl) propylacrylate, preferably. Trimethoxysilylpropylmethacrylate or 3- (dimethoxymethylsilyl) propylmethacrylate.

A more suitable one is the formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
The two groups R ^1s to R ^3s are alkoxy groups, and the remaining groups from R ^1s to R ^3s are alkylene-vinyl groups, especially vinyl or allyl groups).
It is a compound C) having a silicon functional group of.

A more suitable one is the formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
R ^1s is an alkoxy group, R ^2s is an alkyl group, and R ^3s is an alkylene-vinyl group, especially a vinyl or allyl group).
It is a compound C) having a silicon functional group of.

If the reacted compound C) in the prepolymer or composition comprising the prepolymer should be compatible with the silicon functional group, i.e. stable under anhydrous conditions, the trimethoxysilylpropyl glycidyl ether may be an epoxy group and a silicon functional group. A suitable compound C) having a group.

At least one of compounds A), B) or optionally C) may contain a soft segment.

Preferably, at least one of compounds A), B) or optionally C) used as a starting material comprises a segment selected from a polyether group or an organic polysulfide group (aliphatic polysulfide group).

Therefore, in a preferred embodiment, the present invention is a method for preparing a prepolymer containing a urethane group and a curable silicon functional group, wherein at least one of compounds A), B) or optionally C) used as a starting material. It relates to a method comprising a segment in which the species is selected from a polyether group or an organic polysulfide group.

As used herein, the term "organic polysulfide group" or "aliphatic polysulfide group" refers to the reaction of 2-haloethanol, formaldehyde and sodium polysulfide Na ₂ S _x (x ≧ 2), or with bishaloethylformal. It means an aliphatic polysulfide polymer group derived from an aliphatic polysulfide polymer that can be obtained by reacting with sodium polysulfide. 2-Haloethanol is usually 2-chloroethanol and bishaloethylformal is usually bischloroethylformal.

The polyether group or the organic polysulfide group may be contained in compound A), compound B) and / or compound C), preferably compound B) and / or compound C), and more preferably compound B).

The polyether group contains at least two oxyalkylene units.

The polyether group is of the formula
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group containing 2 to 4 carbon atoms, such as ethylene, propylene or butylene. ,
q is 2 to 70, preferably 2 to 40)
Has a unit of.

Desirably, the polyether group is based on polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polytetramethylene glycol, polytetramethylene glycol-polypropylene glycol copolymer or polytetramethylene glycol / polypropylene glycol copolymer.

Desirably, the organic polysulfide group is a reaction of 2-chloroethanol, formaldehyde and sodium polysulfide Na ₂ S _x (x ≧ 2, preferably Na ₂ S ₂ ), or a reaction of bischloroethylformal with Na ₂ S _x . Containing an aliphatic polymer group derived from an aliphatic polysulfide polymer available by, the polysulfide polymer has the general formula for x = 2.
HS- (CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ SS) _r -CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ -SH (IX)
(In the formula, r is about 4 to 25)
Represented by. The polysulfide polymer has an average molecular weight of about 800 to about 5000 g / mol, and the polysulfide polymer is optionally further crosslinked.

For example, a polymer of formula (IX) that is optionally crosslinked is commercially available as a Thiokol® polymer.

Therefore, it is a method for preparing a prepolymer containing a urethane group and a curable silicon functional group, and at least one of the starting materials is a formula.
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group containing 2 to 4 carbon atoms, such as ethylene, propylene or butylene.
q is 2 to 70, preferably 2 to 40)
A segment of a polyether group with a unit of, or
In the segment of organic polysulfide groups containing aliphatic polymer groups derived from aliphatic polysulfide polymers available by the reaction of 2-chloroethanol, formaldehyde and Na ₂ S ₂ or the reaction of bischloroethylformal with Na ₂ S ₂ . There is a polysulfide polymer as a general formula
HS- (CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ SS) _r -CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ -SH (IX)
(In the formula, r is about 4 to 25)
A method is preferred, wherein the polysulfide polymer has an average molecular weight of about 800 to about 5000 g / mol and contains segments in which the polysulfide polymer is optionally further crosslinked.

Generally, a polyether group or an organic polysulfide group does not contain a hydroxy or carboxy group.

Preferably, the prepolymer comprises a segment of a polyether group.

Therefore, it is a method for preparing a prepolymer containing a urethane group and a curable silicon functional group, and at least one of the starting materials is a formula.
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group containing 2 to 4 carbon atoms, such as ethylene, propylene or butylene.
q is 2 to 70, preferably 2 to 40)
A method comprising a segment of a polyether group having a unit of is preferred.

A suitable compound A) used as a starting material containing a segment of a polyether group may be compound A) of formula (II), where Z is the formula.
(VO-) _m V (G1)
(During the ceremony,
V is a C ₂ to C ₄ alkylene group, m is an integer of at least 2)
It is a polyalkoxylen group of. The terminal alkylene group V is attached to a linking group which is one of the groups R ^1b to R ^4b defined above in the present specification.

The compound A) may be prepared in the same manner as described in International Publication No. 2019/034469.

In general, compound A) is used only as a starting material containing a segment of a polyether group.

Therefore, in a preferred embodiment, the present invention is a method for preparing a prepolymer containing a urethane group and a curable silicon functional group.
At least one of compounds A), B) or optionally C) used as a starting material comprises a segment selected from a polyether group or an organic polysulfide group.
However, when compound A) is used as a starting material, compound A) relates to a method that does not contain a segment of an organic polysulfide group.

A suitable compound B) used as a starting material containing a segment of a polyether group may be a compound such as an alkylene-diamine or an alkylene-polyamine containing at least two ether groups.

An alkylene-diamine or an alkylene-polyamine containing at least two ether groups is a polyoxyalkylene amine (polyether amine). The polyoxyalkylene amine is based on, for example, polyethylene glycol, polypropylene glycol, polypropylene glycol / polyethylene glycol copolymer, polytetramethylene glycol, polytetramethylene glycol / polypropylene glycol copolymer or polytetramethylene glycol / polypropylene glycol copolymer.

Suitable polyoxyalkylene diamines are of the formula
H ₂ NR ¹⁵ -O- (R ¹⁶ -O) _s -R ¹⁷ -NH ₂ (X)
(During the ceremony,
R ¹⁵ , R ¹⁶ and R ¹⁷ are C ₂ to C ₄ alkylenes at each appearance independently of each other.
s may be 1 to 70, preferably 1 to 40)
May be defined by.

Preferably, R ¹⁵ to R ¹⁷ are the same C ₂ to C ₄ alkylene, or R ¹⁵ and R ¹⁷ are the same and R ¹⁶ is a different C ₂ to C ₄ alkylene than R ¹⁵ and R ¹⁷ . You may.

C ₂ to C ₄ alkylenes are ethylene, propylene or butylene.

Therefore, in a preferred embodiment, compound B) used as a starting material containing a polyether group is of the formula.
H ₂ NR ¹⁵ -O- (R ¹⁶ -O) _s -R ¹⁷ -NH ₂ (X)
(During the ceremony,
R ¹⁵ , R ¹⁶ and R ¹⁷ are C ₂ to C ₄ alkylenes at each appearance independently of each other.
s may be 1 to 70, preferably 1 to 40)
Polyoxyalkylene diamine.

Suitable polyoxyalkylene amines are trade names Jeffamine®, eg Jeffamine D-230, D-400, D-2000, D-4000, EXTJ-502, EXTJ-511, THF-100 or THF-170 ( Available from Huntsman). Further commercially available polyoxyalkylene amines are, for example, polyetheramines D 230, D 400, D 403, D 2000 (available from BASF).

The polyoxyalkyleneamine may be a polyoxyalkylene triamine, an ethylene oxide, propylene oxide or butylene oxide based or a mixture thereof, and a triol initiator such as glycerol, trimethylolethane. It may be prepared by reacting with propane, trimethylolethane or 1,3,6-hexanetriol and then aminating the terminal hydroxyl group.

Examples of such polyoxyalkylene triamines are Jeffamine T-403, Jeffamine T-50000 and Jeffamine XTJ-509, Polyetheramines T 403 and T 5000.

The corresponding diamine may be similarly prepared starting from the diol initiator. Alternatively, the terminal hydroxy group of the polyether may be aminated. In addition, reductive amination of aldehydes or ketones may give terminal amines. Such reactions are well known in the art.

Therefore, in a preferred embodiment, the compound B) used as a starting material containing a polyether group is polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polytetramethylene glycol, polytetramethylene glycol-polypropylene glycol copolymer or polytetra. A polyether diamine or a polyether triamine based on a methylene glycol / polypropylene glycol copolymer.

Compound B, which is used as a starting material containing a segment of an aliphatic polysulfide group, may be derived from a commercially available Thiokol® polymer. For example, the terminal SH group may be converted to an amine by adding allylamine by a conventional method.

Compound B) may also be used in a form in which the amino group is protected by a protecting group, as described above herein.

Compound B) may be a mixture of different compounds B). Preferably, the compound B) may be a mixture of the compound B) having a silicon functional group and the compound B) containing a segment selected from a polyether group or an organic polysulfide group, preferably a segment of a polyether group.

For example, the weight ratio of the compound B) having a silicon functional group to the compound B) containing a segment selected from a polyether group or an organic polysulfide group may be 5:95 to 50:50.

Preferably, the weight ratio of the compound B) having a silicon functional group to the compound B) containing a segment of a polyether group may be 5:95 to 50:50.

Suitable compounds C) used as starting materials containing segments of polyether or organic polysulfide groups are at least 2 terminal non-aromatic ethylenically unsaturated groups, preferably 2-6 non-aromatic ethylenically. It may be a compound based on a polyether group having an unsaturated group or an organic polysulfide group.

A (meth) acrylate group or a vinyl group, more preferably a compound C) having a (meth) acrylate group is preferable.

The compound C) used as a starting material containing a segment of a polyether group, which is a polyether-di (meth) acrylate or a polyether-tri (meth) acrylate, is most preferred.

Polyether (meth) acrylates are based on, for example, polyethylene glycol, polypropylene glycol, polypropylene glycol / polyethylene glycol copolymers, polytetramethylene glycol, polytetramethylene glycol / polypropylene glycol copolymers or polytetramethylene glycol / polypropylene glycol copolymers.

Suitable polyether (meth) diacrylates are of the formula

(During the ceremony,
R ¹⁸ and R ¹⁹ are independent of each other and are C ₂ to C ₄ alkylene in each appearance.
R ²⁰ and R ²¹ are H or methyl independently of each other
t may be 1 to 70, preferably 1 to 40)
May be defined by.

Preferably, R ¹⁸ and R ¹⁹ are the same C ₂ to C ₄ alkylenes, such as ethylene, propylene or butylene.

Preferably R ²⁰ and R ²¹ are the same, more preferably R ²⁰ and R ²¹ are CH ₃ .

Therefore, in a preferred embodiment, the compound C) used as a starting material containing a polyether group is of the formula.

(During the ceremony,
R ¹⁸ and R ¹⁹ are independent of each other and are C ₂ to C ₄ alkylene in each appearance.
R ²⁰ and R ²¹ are H or methyl independently of each other
t may be 1 to 70, preferably 1 to 40)
Polyether-di (meth) acrylate.

The polyether (meth) acrylate may be a polyether tri (meth) acrylate, may be based on ethylene oxide, propylene oxide or butylene oxide, or a mixture thereof, and triol initiators such as glycerol, etc. It may be prepared by reacting with trimethylolpropane, trimethylolethane or 1,3,6-hexanetriol and then reacting the terminal hydroxyl group with (meth) acrylic acid or a derivative thereof. Reactions are well known in the art.

The corresponding di (meth) acrylate may be similarly prepared starting from the diol initiator. Alternatively, the terminal hydroxy group of the polyether may be reacted with (meth) acrylic acid or a derivative thereof. Such reactions are well known in the art.

Therefore, in a preferred embodiment, the compound C) used as a starting material containing a polyether group is polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, polytetramethylene glycol, polytetramethylene glycol-polypropylene glycol copolymer or polytetra. A polyether-di (meth) acrylate or a polyether-tri (meth) acrylate based on a methylene glycol / polypropylene glycol copolymer.

For example, compound C) used as a starting material containing a segment of an aliphatic polysulfide group of formula (IX) may be derived from a commercially available Thiokol® polymer. The terminal SH group may be reacted with acetylene to obtain a terminal vinyl group. For example, a commercially available epoxy-terminated polysulfide may be converted with (meth) acrylic acid or a derivative thereof.

Compound C) may be a mixture of different compounds C). Preferably, the compound C) may be a mixture of the compound C) having a silicon functional group and the compound C) containing a segment selected from a polyether group or an organic polysulfide group, preferably a segment of a polyether group.

For example, the weight ratio of the compound C) having a silicon functional group to the compound C) containing a segment selected from a polyether group or an organic polysulfide group may be 5:95 to 50:50.

Preferably, the weight ratio of the compound C) having a silicon functional group to the compound C) which is a polyether-di (meth) acrylate or a polyether-tri (meth) acrylate is 5:95 to 50:50. May be good.

According to the method of the invention, compound A) having at least one 5-membered cyclic monothiocarbonate group, and a selection from a primary or secondary amino group or a blocked primary or secondary amino group. Compound B) having at least one amino group (hereinafter referred to as amino group), and compound C having at least one functional group that optionally reacts with the group-SH) are used as starting materials. Being done
At least one of the compounds used as a starting material contains a silicon functional group.

Details of the reaction principles of compounds A), B) and optionally C), as well as the parameters of the reaction, are described in WO 2019/034470 and WO 2019/034473.

The ring system of the 5-membered cyclic monothiocarbonate group of compound A) is opened by the amino group of compound B), resulting in an adduct containing a urethane group and a group-SH.

Additive groups-SH to -SH reactive groups, in particular compounds A) and B) of compound C) or even containing non-aromatic ethylenically unsaturated groups if present. Non-aromatic ethylenically unsaturated or epoxy groups such as 5- (methacryloyloxy) methyl-1,3-oxathiolan-2-one or 5- (acryloyloxy) methyl-1,3-oxathiolan-2-one ( It may be further reacted with compound C), allylamine or aminoalkylvinyl ether (compound B).

The group -SH reacts with the -SH reactive group. For example, the addition of a non-aromatic ethylenically unsaturated group to -SH is known as a Michael addition or a thiol-ene reaction.

It should be mentioned that unreacted groups-SH can oxidize to form disulfide bridges. Such oxidation may occur at room temperature in the presence of oxygen or other oxidants. Disulfide bridges have the potential to improve the mechanical properties of the resulting polymer.

Compound B) is preferably used in an amount having an amino group of 0.8 to 1.2 mol of compound B) per 1 mol of 5-membered cyclic monothiocarbonate group of compound A) in the reaction mixture.

Preferably, the amount of functional group that reacts with -SH is 0.5-1.2 mol per 1 mol of 5-membered cyclic monothiocarbonate group of compound A).

Preferably, the functional group that reacts with -SH is the group of compound C).

Preferably, the starting material is compounds A), B) and C).

Examples of combinations of compounds A), B) and C) that are reacted in the process are listed below, and the functional groups are abbreviated as follows:
Cyclic monothiocarbonate group of compound A): CTC
Primary amino group of compound B): PA
Functional group that reacts with -SH of compound C), A) or B): FG
Silicon functional group: SIL

—— Compound A) with 1 CTC, Compound B) with 1 PA and 1 SIL, and Compound C) with 1-6 FGs, preferably 2-3 FGs.
—— Compound A) with 1 CTC, Compound B) with at least 2 PAs, and Compound C) with 1 FG and 1 SIL,
—— Compound A) with 1 CTC, Compound B) with at least 2 PAs, and Compound B) with 1 PA and 1 SIL,
—— Compound A) with 1 CTC, Compound B) with at least 2 PAs, Compound C) with 1 FG and 1 SIL, and Compound C) with 2 FGs.

Preferably, compounds A), B) and optionally C) are selected to yield a mixture of A), B) and optionally C) which is liquid at 21 ° C., 1 bar. Such mixtures do not require additional solvents to become liquid. In liquid mixtures of A), B) and optionally C), at least one, preferably two, of compounds A), B) and C) are liquids and thus the remaining solid compounds A), B) or Any solvent for C) will suffice.

The mixture of compounds A), B) or optionally C) may contain a solvent. In a preferred embodiment, no solvent is required.

Compounds A), B) and optionally C) are treated by method step b) to give a prepolymer.

Method In step b), compounds A) and B) and optionally C) are reacted to form a prepolymer. Method Step b) is carried out under the elimination of water. To avoid humidity, method step b) may be carried out under an inert gas. The resulting prepolymer contains silicon functional groups that are still curable by moisture, especially humidity.

The reaction between compounds A), B) and optionally C) in step b) generally begins as early as room temperature (about 20-25 ° C) and may complete at room temperature. The reaction may be assisted by raising the temperature of the composition to, for example, 100 ° C. Alternatively or in addition, high energy radiation, such as visible or UV light, may provide any activation energy for the reaction. The advantage of the present invention is that the reaction occurs easily at low temperatures and does not require the supply of significant additional energy, such as high temperature or high energy radiation.

In the case of compound C) having a vinyl or ethynyl group, a radical initiator should be added.

Accordingly, in a further aspect, the invention relates to the prepolymers available by method steps a) and b) as defined in any aspect of the specification.

Therefore, the present invention is a prepolymer containing a urethane group and a curable silicon functional group.
a) Compounds with at least one 5-membered cyclic monothiocarbonate group A),
And compounds with at least one amino group selected from primary or secondary amino groups or blocked primary or secondary amino groups B),
And optionally compound C with at least one functional group that reacts with the group-SH)
The process of using as a starting material,
Here, at least one of the compounds used as a starting material contains a silicon functional group.
And compounds A), B) and optionally C),
b) Available by methods comprising the step of reacting compounds A) and B) and optionally C) under the elimination of water to obtain a prepolymer having a curable silicon functional group. Regarding prepolymers.

The present invention can also provide a composition comprising one or more prepolymers comprising a urethane group and a curable silicon functional group.

Accordingly, in a further aspect, the invention is one or more prepolymers comprising a urethane group and a curable silicon functional group, which are available according to the method steps a) and b) as defined in any aspect of the specification. With respect to the composition comprising.

Therefore, the present invention is a composition comprising one or more prepolymers containing a urethane group and a curable silicon functional group.
a) Compounds with at least one 5-membered cyclic monothiocarbonate group A),
And compounds with at least one amino group selected from primary or secondary amino groups or blocked primary or secondary amino groups B),
And optionally compound C with at least one functional group that reacts with the group-SH)
The process of using as a starting material,
Here, at least one of the compounds used as a starting material contains a silicon functional group.
And compounds A), B) and optionally C),
b) Available by methods comprising the step of reacting compounds A) and B) and optionally C) under the elimination of water to obtain a prepolymer having a curable silicon functional group. Regarding the composition.

The obtained prepolymer contains a urethane group in which a sulfur atom is bonded to oxygen of the urethane group via an ethylene group as a structural element. This structural element has the following general formula:

(In the equation, all dashed bonds may have any possible substituents)
May be represented by.

The structural element corresponds to the reaction product of compound A) and compound B).

Therefore, in a further aspect, the invention
Equation (a)

(During the ceremony,
R ¹ is R ^1a or R ^1b ,
R ² is R ^2a or R ^2b ,
R ³ is R ^3a or R ^3b ,
R ⁴ is R ^4a or R ^4b
R ^1a to R ^4a are independent hydrogens or organic groups with up to 50 carbon atoms, or, instead, R ^2a , R ^4a and two linked carbon atoms are 5 to 5 together. Forming a 10-membered carbon ring,
R ^1b to R ^4b are organic groups that are independent of each other and have hydrogen or up to 50 carbon atoms, and instead, the two carbon atoms of R ^2b , R ^4b and the monothiocarbonate group are also combined. May form a 5- to 10-membered carbon ring.
One of the groups R ^1b to R ^4b is a linking group to Z,
n is an integer of at least 2
Z is an n-valent organic group
R ⁹ is hydrogen or C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ )
The divalent group of, and
(b) Regarding prepolymers containing curable silicon functional groups.

Preferably, the prepolymer is derived from compound A) of formula (I). Therefore, the prepolymer is
Equation (a)

(During the ceremony,
R ^1a to R ^4a are independent hydrogens or organic groups with up to 50 carbon atoms, or, instead, R ^2a , R ^4a and two linked carbon atoms are 5 to 5 together. Forming a 10-membered carbon ring,
R ⁹ is hydrogen or C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ )
Based on, and
(b) Contains curable silicon functional groups.

Preferably, the organic groups of R ^1a to R ^4a are alkyl groups, groups -CH ₂ -OR ^5a or groups -CH ₂ -OC (= O) -R ^6a , and R ^5a and R ^6a are 1 to 10 groups. It is an alkyl group having a carbon atom.

More preferably, all 2 to 4 of R ^1a to R ^4a in the formula (IVa) are hydrogen, and the remaining groups R ^1a to R ^4a are preferably an alkyl group, a group -CH ₂ -OR ^5a or. Group -CH ₂ -OC (= O) -R ^6a is an organic group selected from.

Most preferably, three of R ^1a to R ^4a in formula (IVa) are H, and the remaining groups R ^1a to R ^4a are organic groups, especially alkyl groups, groups -CH ₂ -OR ^5a or groups -CH. ₂ -OC (= O) -R ^6a . In particular, R ^1a or R ^2a are the remaining groups representing organic groups, in particular alkyl groups, groups -CH ₂ -OR ^5a or groups -CH ₂ -OC (= O) -R ^6a .

The group R ⁹ is preferably hydrogen or C ₁ to C ₄ alkyl, more preferably hydrogen.

In a preferred embodiment, the prepolymer is of formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
At least one of the groups R ^1s to R ^3s is an alkoxy group, and the other groups R ^1s to R ^3s are hydrogen, alkyl or alkylene-vinyl groups).
Contains curable silicon functional groups.

More preferably, two or three groups R ^1s to R ^3s are C ₁ to C ₄ alkoxy groups, and the remaining groups R ^1s to R ^3s are C ₁ to C ₄ alkyl groups or C ₁ to C ₂ alkylenes. -Vinyl group, especially one alkyl group.

More preferably, two or three groups R ^1s to R ^3s are alkoxy groups, and any remaining groups R ^1s to R ^3s are alkyl or alkylene-vinyl groups. For example, two or three of the groups R ^1s to R ^3s are methoxy or ethoxy, and any remaining groups R ^1s to R ^3s are methyl, ethyl, vinyl or allyl.

Most preferably, the two groups R ^1s to R ^3s are C ₁ to C ₄ alkoxy groups, and any remaining groups R ^1s to R ^3s are C ₁ to C ₄ alkyl groups.

One of the starting materials may contain a segment selected from a polyether group or an organic polysulfide group.

Thus, in a preferred embodiment, the prepolymer comprises a segment (c) selected from a polyether group or an organic polysulfide group.

The prepolymer preferably contains a segment (c) selected from a polyether group or an organic polysulfide group in an amount of 40 to 95 wt%, more preferably 50 to 90 wt%, and most preferably 55 to 90 wt% based on the total weight of the prepolymer. Include in% quantity.

Therefore, it is a prepolymer containing a urethane group and a curable silicon functional group, and the formula is
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene or butylene.
q is 2 to 70, preferably 2 to 40)
Segment of the polyether group having the unit of (C), or
A segment of an organic polysulfide group containing an aliphatic polymer group derived from an aliphatic polysulfide polymer available by the reaction of 2-chloroethanol, formaldehyde and Na ₂ S ₂ or the reaction of bischloroethylformal with Na ₂ S ₂ ( Prepolymers containing C) are preferred.

A prepolymer containing a urethane group and a curable silicon functional group, wherein the formula is
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group containing 2 to 4 carbon atoms, such as ethylene, propylene or butylene.
q is 2 to 70, preferably 2 to 40)
A prepolymer containing a segment (C) of a polyether group having a unit of is more preferable.

Formula (VIII) derived from compound B) and / or C), especially compound B) or C), particularly compound B), which is a prepolymer containing a urethane group and a curable silicon functional group and is used as a starting material. The prepolymer containing the segment (C) of the polyether group having the unit of is most preferable.

Desirably, the prepolymer comprises a segment of the polyether group (c) in an amount of 50-95 wt%, more preferably 55-90 wt%, based on the total weight of the prepolymer.

Prepolymers generally contain 0.001-0.3 mol of silicon content per 100 g of prepolymer.

Preferably, the silicon content in the prepolymer is 0.001 to 0.4 mol Si, more preferably 0.005 to 0.2 mol Si, and most preferably 0.01 to 0.15 mol Si per 100 g of prepolymer.

The Si content applies to the prepolymer obtained in step b) and the crosslinked polymer finally obtained by method steps b) and b2).

The silicon content (in molars) is calculated based on the amount of starting material used, i.e. the total weight of silicon / starting material.

The prepolymer may be derived from compound A) and compound B), or from compound A), compound B) and compound C).

Prepolymers derived from compounds A) and B) generally contain a disulfide group, a curable silicon functional group and optionally a segment selected from a polyether group or an organic polysulfide group.

For example, the prepolymer may be derived from compound A) of formula (I), monoamines and polyether diamines containing curable silicon functional groups. The prepolymer may be linked by a disulfide group via an SH group.

(During the ceremony,
R ^1a to R ^4a are independent hydrogen or organic groups with up to 50 carbon atoms.
Two or three groups R ^1s to R ^3s are C ₁ to C ₄ alkoxy groups, and the remaining groups R ^1s to R ^3s are C ₁ to C ₄ alkyl groups or C ₁ to C ₂ alkylene-vinyl groups, Especially one alkyl group,
R ⁹ is hydrogen, C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ .
R ¹⁰ is a C ₁ to C ₁₈ alkylene group optionally interrupted by O, S or NR ¹³ .
R ¹² is a divalent polyether group or an organic polysulfide group)
May include.

Prepolymers are preferably formulas (XII) and (XIII).
(During the ceremony,
The two groups R ^1s to R ^3s are C ₁ to C ₄ alkoxy groups, and any remaining groups R ^1s to R ^3s are C ₁ to C ₄ alkyl groups.
R ^1a is an organic group selected from the alkyl group, group -CH ₂ -OR ^5a or group -CH ₂ -OC (= O) -R ^6a .
R ^2a to R ^4a are H,
R ^5a and R ^6a are alkyl groups having 1 to 10 carbon atoms.
R ⁹ is H or methyl or ethyl
R ¹⁰ is C ₂ to C ₈ alkylene, more preferably C ₃ to C ₆ alkylene,
R ¹² is a divalent polyether group)
May include elements of.

For example, the weight ratio of the compound B) having a silicon functional group to the compound B) containing a segment of a polyether group may be 5:95 to 50:50.

The prepolymer may be derived from compound A), compound B) and compound C).

Therefore, in a preferred embodiment, the invention is of the formula.

(During the ceremony,
R ⁹ is hydrogen, C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ .
R ¹⁰ is a C ₁ to C ₁₈ alkylene group, which is optionally interrupted by O, S or NR ¹³ .
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p-valent polyether or organic polysulfide group
R ¹³ is hydrogen or C ₁ to C ₄ alkyl,
p is an integer of 2-6, preferably 2 or 3)
Based on or formula

(During the ceremony,
R ⁹ is hydrogen or C ₁ to C ₄ alkyl,
R ¹⁰ is a C ₁ to C ₁₈ alkylene group, which is optionally interrupted by O, S or NR ¹³ .
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p'valent polyether group or organic polysulfide group.
R ¹³ is hydrogen or C ₁ to C ₄ alkyl,
p'is an integer of 2-5, preferably 2-3)
With respect to prepolymers containing groups of.

Alternatively, p and p'are preferably 2.

The group R ¹⁰ is a C ₁ to C ₁₈ alkylene group or a C ₁ to C ₁₈ alkylene group interrupted at least once, preferably 1, 2 or 3 times by O, S or NR ¹³ .

Preferably, R ¹² is an equation
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group containing 2 to 4 carbon atoms, such as ethylene, propylene or butylene.
q is 2 to 70, preferably 2 to 40)
A divalent or trivalent polyether group having a unit of, or
Divalent or trivalent containing an aliphatic polymer group derived from an aliphatic polysulfide polymer available by the reaction of 2-chloroethanol, formaldehyde and Na ₂ S ₂ or the reaction of bischloroethylformal with Na ₂ S ₂ . It is an organic polysulfide group.

More preferably, R ¹² is an equation
-(R ¹⁴ -O) _q- (VIII)
(During the ceremony,
R ¹⁴ is a divalent linear or branched alkylene group containing 1 to 14 carbon atoms, preferably a linear or branched alkylene group containing 2 to 4 carbon atoms, such as ethylene, propylene or butylene.
q is 2 to 70, preferably 2 to 40)
It is a divalent or trivalent polyether group having the unit of.

In particular, R ¹¹ is a group derived from a vinyl group, an ethynyl group or a (meth) acrylic group, particularly a vinyl group or a (meth) acrylic group, particularly a methacrylic group.

The group of formula (V) contains monomeric units derived from compound A), compound B) and compound C).
Compound A) is of formula (I) and
Compound B) is of the formula R ^1s R ^2s R ^3s Si-R ¹⁰ -NR ⁹ H.
Compound C) is of the formula R ^11' -(R ¹² ) _p ,
R ⁹ is hydrogen, C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ .
R ¹⁰ is a C ₁ to C ₁₈ alkylene group, which is optionally interrupted by O, S or NR ¹³ .
R ^11'is a non-aromatic ethylenically unsaturated group
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p-valent polyether group or a p-valent organic polysulfide group.
R ¹³ is hydrogen or C ₁ to C ₄ alkyl,
p is an integer of 2 to 6, preferably 2 or 3.

The group of formula (VI) comprises a monomer unit derived from compound A), compound B) and compound C).
Compound A) is of formula (I) and
Compound B) is of formula (R ¹² ) _p' -NR ⁹ H and
Compound C) is of the formula R ^1s R ^2s R ^3s Si-R ¹⁰ -R ^11'and
R ⁹ is hydrogen, C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ .
R ¹⁰ is a C ₁ to C ₁₈ alkylene group, which is optionally interrupted by O, S or NR ¹³ .
R ^11'is a non-aromatic ethylenically unsaturated group
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p'valent polyether group or a p'valent organic polysulfide.
R ¹³ is hydrogen or C ₁ to C ₄ alkyl,
p'is an integer of 2-5, preferably 2-3.

Equation (V)
(During the ceremony,
R ⁹ is hydrogen or C ₁ to C ₄ alkyl, preferably hydrogen or methyl, especially hydrogen.
R ¹⁰ is a C ₂ to C ₈ alkylene group, more preferably a C ₂ to C ₆ alkylene group.
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p-valent polyether group
p is an integer of 2 to 3)
Prepolymer,
Or formula (VI)
(During the ceremony,
R ⁹ is hydrogen or C ₁ to C ₄ alkyl, preferably hydrogen or methyl, especially hydrogen.
R ¹⁰ is a C ₂ to C ₈ alkylene group
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p'valent polyether group
p'is an integer of 2 to 3)
Prepolymers are more preferred.

Alternatively, p and p'are preferably 2.

In particular, R ¹¹ is a group derived from a vinyl group, an ethynyl group or a (meth) acrylic group, particularly a vinyl group or a (meth) acrylic group, particularly a methacrylic group.

A prepolymer containing a curable silicon functional group may be further reacted. The prepolymer obtained in step b) is made into the desired form, which is a coating, filler or any other three-dimensional body. Silicon functional groups crosslink each other in the presence of any ambient moisture, such as humidity or supplied moisture. In general, normal humidity is sufficient to finally obtain a fully crosslinked polymer. The cross-linking process may be accelerated by adding more water. For example, water may be added to the prepolymer immediately before the start of step b2).

Therefore, in a further aspect, the present invention is a method of preparing a crosslinked polymer containing a urethane group and a siloxane bond.
The prepolymer obtained in steps a) and b) and step b2) step b) defined in any aspect of the present specification is applied to a surface, a void or a three-dimensional mold, and a silicon functional group is formed by ambient water. The present invention relates to a method including a step of curing.

The polymer obtained in step b2) is a completely cured polymer having a siloxane bond.

Accordingly, in a further aspect, the invention is a crosslinked polymer comprising a monomer unit derived from Compound A), Compound B) and optionally Compound C) as defined in any aspect of the specification.
The polymer relates to a crosslinked polymer containing 0.001-0.3 mol of silicon per 100 g of crosslinked polymer.

Preferably, the silicon content in the crosslinked polymer is 0.001 to 0.4 mol Si, more preferably 0.005 to 0.2 mol Si, and most preferably 0.01 to 0.15 mol Si per 100 g of the crosslinked polymer.

In a further aspect, the invention applies the prepolymer obtained in steps a) and b), as defined in any aspect herein, and step b2) step b) to a surface, void or three-dimensional template. The present invention relates to a crosslinked polymer that can be obtained by a method including a step of curing a silicon functional group with ambient water.

The prepolymers of the present invention may be used in compositions for a variety of uses, such as one-component encapsulants or adhesive compositions. Preferably, the prepolymer is used in a one-component encapsulant or adhesive composition.

Accordingly, the present invention relates to compositions comprising prepolymers as defined in any aspect of the specification.

In a preferred embodiment, the invention relates to a one-component encapsulant or adhesive composition comprising a prepolymer as defined in any aspect of the specification.

In general, a composition, preferably a one-component encapsulant or adhesive composition, encloses the prepolymer with an encapsulant or adhesive on the substrate, or bonds the two substrates together. It is included in sufficient amounts to allow for, for example, in an amount of 10-100 wt%, preferably 20-70 wt% based on the total weight of the composition.

The one-component encapsulant or adhesive composition generally contains additives well known in the art. Additional solvents may be present to reduce the viscosity.

If present, the solvent should be non-aqueous at the intended use level and non-reactive with the prepolymer. Examples include tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, methylethylketone, acetone, heptane, toluene, trichloroethane, methyl acetate, butyl acetate, t-butyl acetate and the like. A mixture of the above solvents can also be used. The solvent may be present in an amount of 0-30 wt%, preferably 0-15 wt% based on the total weight of the composition.

Examples of suitable additives are desired or required for the intended end use of catalysts, radical initiators, dehydrating agents, plasticizers, fillers, thixotropic modifiers, adhesion promoters, stabilizers, or crosslinked polymers. Additives such as colorants or dielectrics.

Examples of suitable catalysts, preferably silanol condensation catalysts, are, for example, organotin compounds such as tin 2-ethylhexanoate (II), dilaureate diactyltin, dibutyltin dilaurate, dibutyltin maleate or dibutyltin diacetate, fluorine. Containing compounds such as triethoxyfluorosilane, tertiary amines such as 1,8-diazabicyclo (5.4.0) undeca-7-ene (DBU), 1-azabicyclo [3.3.0] octane, 1,4-diazabicyclo [ 2.2.2] Octane, trialkylamines or N-substituted piperidines, titanates such as alkyl titanates or organic silicon titanates or combinations thereof.

Preferably, the silanol condensation catalyst is generally in an amount sufficient to cure the polymer upon exposure to humidity, eg 0.005-5 wt%, preferably 0.1-2 wt%, based on the total weight of the prepolymer to be cured. Exists in. The catalyst may be added during or after the preparation of the prepolymer.

Alternatively, there is preferably no silanol condensation catalyst.

Examples of suitable dehydrating agents are, for example, 0-5 wt%, preferably 0-3 wt% or 0.1-2 wt% of vinylsilane, such as vinyltrimethoxysilane or vinyltriethoxysilane, based on the total weight of the composition. ..

Examples of suitable plasticizers are, for example, phthalates such as dioctyl phthalate, dibutyl phthalate, diundecyl phthalate or dibutyl phthalate benzyl phthalate, adipate such as dialkyl adipate, phosphate, such as trioctyl phosphate or tricredyl phosphate, or sulfonamides. For example, N-butyl-p-toluene-sulfonamide. The plasticizer is preferably used in an amount of 0-30 wt%, more preferably 5-20 wt%, based on the total weight of the composition.

Examples of suitable fillers are, for example, reinforcing fillers such as silica, fumed silica such as Aerosol®, silica airgel, clay, calcium carbonate, titanium dioxide, talc, magnesium carbonate or glass fiber. Examples of colorants are, for example, pigments or pigments such as carbon black, preferably transparent pigments or pigments. Examples of dielectrics are, for example, graphite or carbon black. The total amount of filler, colorant and dielectric is generally about 0-60 wt%, preferably 5-50 wt% based on the total weight of the composition.

Examples of suitable thixotropic agents are, for example, alumina, limestone, zinc oxide, sulfur oxide, calcium carbonate, perlite, NaCl or cyclodextrin. The total amount of thixotropic agent is generally about 0-10 wt%, preferably 0-2 wt%, more preferably 0.1-2 wt%, based on the total weight of the composition.

Suitable stabilizers are, for example, biocides, UV stabilizers, heat stabilizers or antioxidants. Examples are sterically hindered phenols, thioethers, substituted benzotriazoles, HALS-type sterically hindered amines or combinations thereof. Stabilizers are generally present in an amount of 0-2.5 wt% based on the total weight of the composition.

Additives may be added to the prepolymer before, during or after their preparation. Additives should be added in dry form under virtually anhydrous conditions. The components of the composition may be blended in a suitable mixer in an inert atmosphere in the absence of oxygen and ambient moisture. Once formulated with a one-component encapsulant or adhesive composition, it is packaged in a suitable container to protect it from ambient moisture and oxygen.

Various substrates can be sealed or bonded using the one-component encapsulant or adhesive composition of the present invention. Examples include plastics, glass, wood, ceramics, metals and coated substrates such as primer coated substrates. The morphology may be a surface, voids or a three-dimensional mold.

The adhesive composition is applied to the substrate and then the adhesive composition on the first substrate is brought into contact with the second substrate.

Generally, the one-component encapsulant or adhesive composition is applied to the substrate at ambient temperature in the presence of ambient moisture. Exposure to ambient moisture is sufficient to cause curing of the encapsulant or adhesive composition, resulting in the crosslinked polymers of the present invention. The cured product becomes tack-free in a relatively short period of time.

The one-component encapsulant or adhesive composition may be applied to a wet or moist surface.

Curing may be accelerated by adding additional moisture or heat. Preferably the encapsulant or adhesive composition is formulated so that the working time is up to 3-8 hours depending on the moisture content. Complete curing may require up to 5 days.

Crosslinked polymers are suitable for use as a component of sealants or adhesives.

Accordingly, in a further aspect, the invention relates to the use of a crosslinked polymer as defined in any of the above embodiments herein as a component of a sealant or adhesive.

For example, the compositions of the present invention are suitably applied to construction, construction, transportation, for example, the automobile industry.

By the method of the present invention, a silyl-modified polymer having urethane and sulfur functionality can be easily and economically obtained. All of these groups combine particularly desired properties that are useful in producing sealants and adhesives.

The prepolymer of the present invention is easily and economically available by the method of the present invention. The method can be carried out at room temperature without additional energy supply. The method does not require the use of starting materials with isocyanate or mercaptan groups.

The method prepares polymer hybrids with benefits obtained from the content of various products, especially sulfur, urethane and silyl crosslinks, eg, mechanical properties in combination with chemical resistance, barrier properties, antistatic and corrosion resistance. Will be possible.

In particular, crosslinked polymers having a soft segment of a polyether group or an organic polysulfide group have good elastic properties, high flexibility, and transparency as long as they are filled with a transparent filler or pigment.

Curing can be carried out rapidly at room temperature without significant shrinkage, resulting in a tack-free product. In addition, crosslinked polymers exhibit a high index of refraction, which is beneficial, for example, in glass substrates.

Cross-linking derived from the inorganic silicon functional groups present in the prepolymer facilitates tough adhesion of the cross-linked polymer hybrid to various substrates, such as glass or metal, which normally requires a primer.

The nature of the silyl substituents in the prepolymer and the concentration of the silyl groups can make the properties suitable for use in the preparation of single component encapsulants or adhesive compositions. The prepolymer may be obtained as a viscous and storable material after pre-curing in a nitrogen atmosphere.

The prepolymer remains stable for a long period of time under anhydrous storage conditions. Further, the alkoxy-hydrolyzable group on the terminal silicon functional group is preferred over other hydrolyzable groups because it produces an inert by-product of the alcohol in the presence of moisture upon curing.

The one-component encapsulant or adhesive composition does not have the drawbacks of in-situ mixing of viscous materials that once mixed, they must be used quickly before becoming unmanageable.

The definitions and preferences given to the pigments referred to above herein apply to any combination and any combination for other aspects of the invention.

Here, the present invention will be described in more detail with reference to the following examples. These examples should not be construed as limiting. Unless otherwise stated, "%" is always% by weight (wt%).

[Example]
Shore A hardness The hardness was measured by the Shore A hardness tester HDA100-1 (Sauter GmbH). A 3 mm sample was placed on a hard surface and the hardness was tested at 4 different locations on the sample surface. The average of four values is shown as the hardness for comparison between different samples.

Viscosity Viscosity was measured in a plate-plate (25 mm) rotation experiment using an MCR301 rheometer (Anton Paar GmbH). The shear rate was increased from 1 to 250 1 / s at a constant temperature.

Glass transition temperature T _g
The glass transition temperature was determined by differential scanning calorimetry (DSC) in an air atmosphere over a temperature range of -170 to 600 ° C. at a heating rate of 10 k / min (Perkin-Elmer Pyris-1).

Thermogravimetric analysis (TGA)
The starting temperature T _onset was determined by STA 449 F5 (Netzsch Geraetebau GmbH) in an air atmosphere at a heating rate of 10 K / min over a temperature range of 50-650 ° C.

Component compound A used in the examples
A-1 5- (butoxymethyl) -1,3-oxathiolan-2-one prepared according to Example 3 of International Publication No. 2019/034469.

A-2 5-Methyl-1,3-oxathiolan-2-one prepared according to Example 1 of International Publication No. 2019/034469.

Compound B
B-1 Jeffamine THF-170 amine (M _n approx. 1700 g / mol)
Amines based on the [Poly (Tetramethylene Ether Glycol)] / (Polypropylene Glycol) Copolymer available from Huntsman
Jeffamine THF-170 (white solid at room temperature) was melted at 50 ° C. and cooled again to room temperature for use in the examples. It remained liquid for several hours.

B2 3-aminopropyldimethoxymethylsilane

B3 4,9-dioxa-1,12-dodecane diamine

Compound C
C-1 3- (dimethoxymethylsilyl) propyl methacrylate

C-2 3- (trimethoxysilyl) propyl methacrylate

C-3 Poly (Propylene Glycol) Dimethacrylate (M _n ≒ 560 g / mol)

C-4 Diurethane Dimethacrylate

Synthesis example 1
C-5 polytetrahydrofuran dimethacrylate (PTHF-DMA, M _n about 3200 g / mol)
Polytetrahydrofuran (M _n about 3000 g / mol, 60 g, 20 mmol) was heated to 90 ° C. in an open flask. Then, MgO nanoparticles (average particle size: 20 nm, 330 mg, about 0.5 wt%) were added with stirring. After 10 minutes of stirring, methacrylic anhydride (6.3 mL, 42 mmol, 2.1 eq) was added to the open flask at once. After 2 hours, the mixture was cooled to room temperature, diluted with dichloromethane (150 mL) and extracted 3 times with saturated NaHCO ₃ aqueous solution. The separated organic layer was dried over Na ₂ SO ₄ until the mixture was clarified. The solvent was removed under reduced pressure to give PTHF-DMA (60 g, approximately 95% yield) as a clear colorless oil, which was solidified at room temperature to a white solid. The product was melted at 50 ° C., cooled to room temperature again and used in the examples. It remained liquid for several hours.

Synthesis Example 2: Synthesis of the compound of formula (VIIa) by the method described in WO 2019/034469.
First step: Synthesis of [1- (chloromethyl) -2- (3-trimethoxysilylpropoxy) ethyl] carbonochloride
A 0.25 L stirring tank glass reactor equipped with two condensers (-30 ° C and -78 ° C (dry ice)), a phosgene dip tube and an internal thermometer was purged with dry nitrogen overnight. Then, 113.6 g (0.47 mol, 1.00 eq) of 3-glycidoxypropyltrimethoxysilane was introduced under a nitrogen atmosphere. Cooling of the tank reactor was turned on and adjusted to 15 ° C. When the reactor reached this temperature, 1.30 g (0.005 mol, 1.00 mol%) of tetrabutylammonium chloride (TBACl) was suspended in the starting material. Then phosgene (61 g in total, 0.67 mol, 1.31 eq) was added to the reactor via a dip tube. The temperature of the reaction mixture was kept below 20 ° C. by continuously monitoring and carefully adjusting the rate of addition of phosgene. The addition took approximately 4 hours overall. After the addition of phosgene was complete, the initial cooling of the reactor was turned off and the reactor was slowly brought to room temperature. The reaction mixture was then stirred at room temperature for an additional 2 hours. Finally, the reaction mixture was stripped with dry argon at room temperature and phosgene was desorbed within 4 hours. The resulting colorless oil (151 g, 0.45 mol, 96% yield, position isomer purity:> 95%) was used directly for the formation of thiocarbonates without further purification.

Second step: Synthesis of 5- (3-trimethoxysilylpropoxymethyl) 1,3-oxathiolan-2-one
[1- (Chloromethyl) -2- (3-trimethoxysilylpropoxy) ethyl] Carbonochloridate (20 g, 0.06 mol) and acetonitrile (50 mL), KPG crescent stirrer, dropping funnel, thermometer and reflux condensation Placed in a 250 mL four-necked round-bottom flask equipped with a vessel. The solution was cooled to 0 ° C. in an ice bath, then solid Na ₂ S (1 eq) was added slowly to maintain the temperature at 5 ° C. After completion of the addition, the ice bath was removed and the reaction mixture was warmed to room temperature. The suspension was filtered with stirring for 4 hours and the solvent was removed under reduced pressure. The crude cyclic thiocarbonate was obtained as a clear oil (17 g, 95%).

[Example 1]
5-Methyl-1,3-oxathiolan-2-one (295 mg, 2.5 mmol, 1 eq)
Jeffamine THF-170 (2.13 g, 1.25 mmol, 0.5 eq)
3- (Dimethoxymethylsilyl) propylmethacrylate (349 mg, 1.50 mmol)
Poly (propylene glycol) dimethacrylate (M _n approx. 560 g / mol, 280 mg, 0.5 mmol)

All substances were mixed in a glass vial using a spatula at room temperature (about 20-25 ° C). After homogenization, triethoxyfluorosilane (1 drop, about 1 mol%) as a silanol condensation catalyst was added under a nitrogen atmosphere, the mixture was mixed again and at 80 ° C. in a glass vial with a lid filled with nitrogen. saved. After 24 hours at 80 ° C., the resulting viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity (defined as cure start time). The tip of the spatula was brought into contact with the surface of the sample at 10 minute intervals. The time until the surface of the sample did not adhere to the spatula was defined as the skin formation time. The cured polymer sample was removed from the mold after 48 hours to give a nearly colorless, completely clear, highly flexible, bendable with close bending radii product.

[Example 2]
5-Methyl-1,3-oxathiolan-2-one (295 mg, 2.5 mmol, 1 eq)
Jeffamine THF-170 (2.13 g, 1.25 mmol, 0.5 eq)
3- (Trimethoxysilyl) propyl methacrylate (310 mg, 1.25 mmol)
Poly (propylene glycol) dimethacrylate (M _n approx. 560 g / mol, 350 mg, 0.5 mmol)

All substances were mixed in glass vials using a spatula at room temperature. After homogenization, the mixture was stored at 80 ° C. in a glass vial with a lid filled with nitrogen. After 24 hours at 80 ° C., the resulting viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity (defined as cure start time). The tip of the spatula was brought into contact with the surface of the sample at 10 minute intervals. The time until the surface of the sample did not adhere to the spatula was defined as the skin formation time. The cured polymer sample was removed from the mold after 48 hours to give a nearly colorless, completely clear, highly flexible, near-bending radius bendable product.

[Example 3]
5-Methyl-1,3-oxathiolan-2-one (590 mg, 5.0 mmol)
Diurethane dimethacrylate (1.18 g, 2.5 mmol)
3-Aminopropyldimethoxymethylsilane (816 mg, 5.0 mmol)

All substances were mixed in glass vials using a spatula at room temperature. After homogenization, triethoxyfluorosilane (1 drop, about 1 mol%) was added under a nitrogen atmosphere, the mixture was mixed again and stored at 80 ° C. in a glass vial with a lid filled with nitrogen. After 24 hours at 80 ° C., the resulting viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity. The cured polymer sample was removed from the mold after 96 hours to give a colorless, completely transparent, highly flexible, close bend radius product.

[Example 4]
5-Methyl-1,3-oxathiolan-2-one (590 mg, 5.0 mmol)
Diurethane dimethacrylate (1.18 g, 2.5 mmol)
3-Aminopropyldimethoxymethylsilane (653 mg, 4.0 mmol)
4,9-dioxa-1,12-dodecanediamine (102 mg, 0.5 mmol)

All substances were mixed in a glass vial using a spatula at room temperature. After homogenization, triethoxyfluorosilane (1 drop, about 1 mol%) was added under a nitrogen atmosphere, the mixture was mixed again and stored at 80 ° C. in a glass vial with a lid filled with nitrogen. After 24 hours at 80 ° C., the resulting viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity. The cured polymer sample was removed from the mold after 96 hours to give a colorless, completely transparent, highly flexible, close bend radius product.

[Example 5a]
5- (Butoxymethyl) -1,3-oxathiolan-2-one (228 mg, 1.2 mmol)
Polytetrahydrofuran dimethacrylate (PTHF-DMA, 1.86 g, 0.6 mmol)
3-Aminopropyldimethoxymethylsilane (157 mg, 0.96 mmol)
Jeffamine THF-170 (204 mg, 0.12 mmol)

All substances were mixed in a glass vial using a spatula at room temperature. After homogenization, triethoxyfluorosilane (1 drop, about 1 mol%) was added under a nitrogen atmosphere, the mixture was mixed again and stored at 80 ° C. in a glass vial with a lid filled with nitrogen. After 24 hours at 80 ° C., the resulting viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity. The cured polymer sample was removed from the mold after 48 hours to give a colorless, completely transparent, highly flexible, near-bending radius bendable product.

[Example 5b]
The procedure of Example 5a was repeated except that 118 mg (0.72 mmol) of 3-aminopropyldimethoxymethylsilane and 480 mg (0.24 mmol) of Jeffamine THF-170 were used.

[Example 6a]
5- (Butoxymethyl) -1,3-oxathiolan-2-one (951 mg, 5 mmol)
Poly (Propylene Glycol) Dimethacrylate (1.40 g, 2.5 mmol)
3-Aminopropyldimethoxymethylsilane (653 mg, 4 mmol)
Jeffamine THF-170 (850 mg, 0.5 mmol)

All substances were mixed in a glass vial using a spatula at room temperature. After homogenization, triethoxyfluorosilane (1 drop, about 1 mol%) was added under a nitrogen atmosphere, the mixture was mixed again and stored at 80 ° C. in a glass vial with a lid filled with nitrogen. After 24 hours at 80 ° C., the resulting viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity. The cured polymer sample was removed from the mold after 48 hours to give a colorless, completely transparent, highly flexible, near-bending radius bendable product.

[Example 6b]
The procedure of Example 6a was repeated except that 3-aminopropyldimethoxymethylsilane in an amount of 490 mg (3 mmol) and Jeffamine THF-170 in an amount of 1.70 mg (1 mmol) were used.

[Example 6c]
The procedure of Example 6a was repeated except that 408 mg (2.5 mmol) of 3-aminopropyldimethoxymethylsilane and 2.13 mg (1.25 mmol) of Jeffamine THF-170 were used.

[Example 7]
5-Methyl-1,3-oxathiolan-2-one (1.48 g, 12.5 mmol)
Jeffamine THF-170 (10.65 g, 6.25 mmol)
3- (Trimethoxysilyl) propyl methacrylate (930 mg, 3.75 mmol)
Poly (Propylene Glycol) Dimethacrylate (2.45 g, 4.38 mmol)
Vinyltrimethoxysilane (310 mg, 2.0 wt% of polymer)
Tin 2-ethylhexanoate (II) (80 mg, 0.5 wt% of polymer)
Aerosil® R972 (2.33g, 15wt% of polymer)

All liquids (Jeffamine THF-170 preheated to 45 ° C.) were mixed at room temperature using a spatula in a cup suitable for high speed mixers. After homogenization, Aerosil R 972 (filler) was added to the mixture. The closed cup was placed in a high speed mixer at 2800 rpm for 1 minute. Then, the cup was filled with nitrogen and stored at 65 ° C. After 24 hours at 65 ° C., the viscous prepolymer was transferred into an aluminum mold (60 mm × 17 mm × 3 mm). The mold was stored at room temperature and ambient air humidity. The cured polymer sample was removed from the mold after 48 hours. The resulting material is colorless and completely transparent, very flexible and flexible with a close bending radius.

The polymers obtained in Examples 1-4, 5a, 5b, 6a-6c, 7 and 8 were analyzed and the results are shown in Tables 1 and 2.

The prepolymers obtained in Examples 1 to 4 and 6a to 6c are analyzed, and the results of viscosity analysis are listed in Tables 3 and 4.

[Example 8]
Preparation of Adhesive Glass Plate Example 7 was repeated to obtain a prepolymer. Viscous prepolymer was applied from a syringe onto a glass plate (7.5 cm x 2.5 cm x 1 mm). A second glass plate was placed on the prepolymer and the two glass plates were pressed together. The polymer layer was 6.6 μm.

The transmission of the adhesive glass plate was measured at 200-1000 nm. The glass plates adhered with the polymer of Example 8 have approximately the same transmission and perfection for visible light within the measurement error, as compared to the transmission of two identical glass plates without adhesive. Shows transparency (see Figure 1).

Claims (19)

A method for preparing a prepolymer containing a urethane group and a curable silicon functional group.
a) Compounds with at least one 5-membered cyclic monothiocarbonate group A),
And compounds with at least one amino group selected from primary or secondary amino groups or blocked primary or secondary amino groups B),
And optionally compound C with at least one functional group that reacts with the group-SH)
The process of using as a starting material,
Here, at least one of the compounds used as a starting material contains a silicon functional group.
And compounds A), B) and optionally C),
b) A method comprising a step of reacting compounds A) and B) and optionally C) under the elimination of water to obtain a prepolymer having a curable silicon functional group. Compound A) has the formula

(During the ceremony,
R ^1a to R ^4a are independent hydrogen or organic groups with up to 50 carbon atoms.
Alternatively, the two carbon atoms of the R ^2a , R ^4a and thiocarbonate groups may also be combined to form a 5-10 membered carbon ring).
Compound or formula

(During the ceremony,
R ^1b to R ^4b are independent hydrogen or organic groups with up to 50 carbon atoms.
Alternatively, the two carbon atoms of the R ^2b , R ^4b and monothiocarbonate groups may also be combined to form a 5-10 membered carbon ring.
One of the groups R ^1b to R ^4b is a linking group to Z,
n is an integer of at least 2
Z is an n-valent organic group)
The method according to claim 1, which is a compound of the above. The method of claim 1 or 2, wherein compound B) comprises 1 to 5 amino groups, preferably 1, 2 or 3 amino groups. -The method of claim 1, 2 or 3, wherein the functional group of compound C) that reacts with SH is a non-aromatic ethylenically unsaturated group. The method according to any one of claims 1 to 4, wherein the compound B) or the compound C) contains a silicon functional group. The silicon functional group has the formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
Two or three groups R ^1s to R ^3s are alkoxy groups, and the remaining groups R ^1s to R ^3s are alkyl or alkylene-vinyl groups).
The method according to any one of claims 1 to 5, which is an alkoxysilane group of the above. 17. the method of. The method according to any one of claims 1 to 7, wherein the mixture of compounds A), B) and optionally C) is a liquid at 21 ° C. and 1 bar. The method according to any one of claims 1 to 8, wherein the content of silicon in the prepolymer is 0.001 to 0.3 mol of silicon per 100 g of the prepolymer. A prepolymer containing a urethane group and a curable silicon functional group, which can be obtained by the method according to any one of claims 1 to 9 steps a) and b). Equation (a)

(During the ceremony,
R ¹ is R ^1a or R ^1b ,
R ² is R ^2a or R ^2b ,
R ³ is R ^3a or R ^3b ,
R ⁴ is R ^4a or R ^4b
R ^1a to R ^4a are independent hydrogens or organic groups with up to 50 carbon atoms, or, instead, R ^2a , R ^4a and two linked carbon atoms are 5 to 5 together. Forming a 10-membered carbon ring,
R ^1b to R ^4b are organic groups that are independent of each other and have hydrogen or up to 50 carbon atoms, and instead, the two carbon atoms of R ^2b , R ^4b and the monothiocarbonate group are also combined. May form a 5- to 10-membered carbon ring.
One of the groups R ^1b to R ^4b is a linking group to Z,
n is an integer of at least 2
Z is an n-valent organic group
R ⁹ is hydrogen or C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ )
Based on, and
(b) Prepolymer containing curable silicon functional group. The silicon functional group has the formula
-SiR ^1s R ^2s R ^3s (III)
(During the ceremony,
Two or three groups R ^1s to R ^3s are alkoxy groups, and the remaining groups R ^1s to R ^3s are alkyl or alkylene-vinyl groups).
The prepolymer according to claim 11, which is the basis of the above. The prepolymer according to claim 11 or 12, preferably comprising a segment (c) selected from a polyether group or an organic polysulfide group in an amount of 50-95 wt% based on the total weight of the prepolymer. formula

(During the ceremony,
R ⁹ is hydrogen, C ₁ to C ₄ alkyl or C ₁ to C ₄ alkylene-N (C ₁ to C ₄ alkyl) ₂ .
R ¹⁰ is a C ₁ to C ₁₈ alkylene group, the alkylene group optionally interrupted by O, S or NR ¹³ .
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p-valent polyether or organic polysulfide group
R ¹³ is hydrogen or C ₁ to C ₄ alkyl,
p is an integer of 2-6, preferably 2 or 3)
Based on or formula

(During the ceremony,
R ⁹ is hydrogen or C ₁ to C ₄ alkyl,
R ¹⁰ is a C ₁ to C ₁₈ alkylene group, the alkylene group optionally interrupted by O, S or NR ¹³ .
R ¹¹ is a group derived from a non-aromatic ethylenically unsaturated group.
R ¹² is a p'valent polyether group or organic polysulfide group.
R ¹³ is hydrogen or C ₁ to C ₄ alkyl,
p'is an integer of 2-5, preferably 2-3)
The prepolymer according to claim 12 or 13, which comprises a group of. A composition comprising the prepolymer as defined in any one of claims 11-14, preferably a one-component encapsulant or adhesive composition. Use of the prepolymer as defined in any one of claims 11-14 or the composition as defined in claim 16 as a component of a one-component encapsulant or adhesive composition. A crosslinked polymer containing a monomer unit derived from compound A), compound B) and optionally compound C) defined in any one of claims 1 to 9, wherein the polymer is 0.001 to 0.3 per 100 g of the crosslinked polymer. A crosslinked polymer containing mol of silicon. A method for preparing a crosslinked polymer containing a urethane group and a siloxane bond.
The prepolymer obtained in steps a) and b) defined in any one of claims 1 to 10 and step b2) step b) is applied to a surface, voids or a three-dimensional mold, and silicon functionalized by ambient moisture. A method comprising the step of curing a group. A crosslinked polymer available by the method defined in claim 18.

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